CN101573324B - Arylamine compounds and electronic devices - Google Patents

Arylamine compounds and electronic devices Download PDF

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CN101573324B
CN101573324B CN2006800568600A CN200680056860A CN101573324B CN 101573324 B CN101573324 B CN 101573324B CN 2006800568600 A CN2006800568600 A CN 2006800568600A CN 200680056860 A CN200680056860 A CN 200680056860A CN 101573324 B CN101573324 B CN 101573324B
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phenyl
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negative electrode
phenylbenzene
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CN101573324A (en
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陈志宽
甄常刮
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Agency for Science Technology and Research Singapore
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Abstract

There is provided conductive organic arylamine compounds. The compounds may be prepared as films and such films may be used as a hole transporting layer, an emissive layer or an electron transporting layer in organic light emitting devices.

Description

Aromatic amine compound and electron device
Technical field
The present invention relates generally to conductive organic compound, in particular to the electroluminescent organic compound, and the electron device that comprises described compound.
Background technology
The electroluminescent organic materials can be divided into two classes: conjugated polymers and organic molecule.
The polymer electroluminescence organic materials comprise the p-phenylene vinylene (, poly-fluorenes (and their derivative.Electroluminescent polymer is attractive is the solution workability because of them, and this is a kind of relative cost effective means for the electron device that manufacture comprises the electroluminescent organic materials.
But, because polymer luminescent material often contains at a certain amount of textural defect on main polymer chain, the by product that produces in polymerization process and remains in the end group on polymer chain, so these materials are difficult to realize high purity.Efficiency and life-span that all these impurity in described polymkeric substance preparation and/or defect can affect the electron device that comprises the polymer electroluminescence organic materials.
Small molecules represents another kind of luminescent material and or as luminiferous material or as charge transfer material and by being widely used in organic luminescent device, for example Organic Light Emitting Diode (OLED).Due to the purification process that has used for example distillation or recrystallization method, so can produce quite pure small molecules luminescent material, this compares with luminescence polymer is an advantage.
But, comprise micromolecular device and generally use evaporating deposition technique to carry out, this be not often cost effectively and be unsuitable for scale operation.Usually, solution processing is a kind of technology of lower cost and is more suitable for a large amount of and produces, and also can be more suitable in preparing the needed more large size of large-sized monitor film fast.
Multilayer device is known, and generally with following each layer, forms: hole transmission layer, luminescent layer and electron transfer layer also may comprise hole injection layer and/or electron injecting layer.
But many present luminous organic materials, comprise polymkeric substance and small molecules, generally all has unbalanced charge transmission.Generally speaking, luminescent material is merely able to conduct a kind of electric charge carrier, or hole or electronics, but is not generally that both have concurrently.For example, the p-phenylene vinylene that p-phenylene vinylene or alkoxyl group replace is good hole transport body, and three-(oxine) aluminium (III) are (Alq3) a kind of electric transmission body.Unbalanced electric charge transmission causes lower device efficiency in the OLED device.
A solution of electric charge carrier in balancing device is that electric transmission part and hole transport part both are attached in a structure to construct a kind of bipolar materials; Perhaps in main truss, these two parts are linked together or these two parts are connected on main truss respectively.
Although developed some this bipolar materials, up to now, the device performance based on this material of reporting is still unsatisfactory.
Therefore, need the new material of exploitation, it can be used in the organic luminous layer in electroluminescent device.
Summary of the invention
one aspect of the present invention provides the compound of general formula (I):
Figure G2006800568600D00021
wherein, Ar 1, Ar 2and Ar 3be independently separately: not necessarily by side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched heterochain thiazolinyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, the arylidene that one or more group in aryl and heteroaryl replaces, heteroarylidene (heteroarylene), arylidene vinylidene (arylene vinylene), heteroarylidene vinylidene (heteroarylene vinylene), arylidene ethynylene (arylene ethynylene) or heteroarylidene ethynylene (heteroaryleneethynylene), Ar 4and Ar 5be independently separately: not necessarily by side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched heterochain thiazolinyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, the arylidene that one or more group in aryl and heteroaryl replaces, heteroarylidene, the arylidene vinylidene, the heteroarylidene vinylidene, arylidene ethynylene or heteroarylidene ethynylene, Ar 6and Ar 7be independently separately: not necessarily by side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched mixing ] arylidene, heteroarylidene, arylidene vinylidene, heteroarylidene vinylidene, arylidene ethynylene or heteroarylidene ethynylene that one or more group in alkenyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, aryl and heteroaryl replaces, and Ar 6and Ar 7in at least one be electrophilic Ar group, by one or more electron-withdrawing substituent, replaced, or the electrophilic Ar group that is replaced by one or more electron-withdrawing substituent, with m, n, p, r, s, x and y be independently 1～20 integer separately.
The embodiment of the compound of general formula (I) is electroluminescent, and therefore can be used as the organic layer in organic electroluminescence device, and can be used to form luminescent layer, electric charge injection layer, charge transport layer or hole blocking layer.
Advantageously, partly both form above-claimed cpd by hole transport part and electric transmission, and these parts combine makes this compound have the bipolarity transfer function.Simultaneously, these compounds are solution processable, and can easily be purified to relatively high degree.
Therefore, another aspect of the present invention provides a kind of film that comprises compound of the present invention.
Another aspect of the present invention provides a kind of device, and it comprises anode, negative electrode and film of the present invention, and this film is arranged between described anode and negative electrode.
One side more of the present invention provides a kind of device, and it comprises anode, is arranged on the luminescent layer that comprises compound of the present invention on this anode and is arranged on the negative electrode on this luminescent layer.
Another aspect of the present invention provides a kind of device, it comprises anode, be arranged on hole transmission layer on this anode, be arranged on luminescent layer on this hole transmission layer, be arranged on the electron transfer layer on this luminescent layer and be arranged on the negative electrode on this electron transfer layer, and wherein the one deck at least in hole transmission layer, luminescent layer and electron transfer layer contains compound of the present invention.
Another aspect of the present invention provides a kind of device, it comprises anode, be arranged on hole injection layer on this anode, be arranged on hole transmission layer on this hole injection layer, be arranged on luminescent layer on this hole transmission layer, be arranged on the electron transfer layer on this luminescent layer and be arranged on hole blocking layer on this electron transfer layer, be arranged on electron injecting layer on hole blocking layer, be arranged on the negative electrode on electron injecting layer, and wherein the one deck at least in hole transmission layer, luminescent layer or electron transfer layer contains compound of the present invention.
When checking by reference to the accompanying drawings the description of following specific embodiment of the invention scheme, other side of the present invention and feature will become obvious for those skilled in the art.
The accompanying drawing explanation
In the accompanying drawings, it is only with the mode of the example embodiment of the present invention of explaining.
Fig. 1 is the schematic diagram of general formula (I), shows electric transmission, hole transport and luminous adjusting part in general formula (I);
Fig. 2 is the schematic diagram of synthesis mechanism of some compound of explanation general formula (I);
Fig. 3 is the schematic diagram of a single layer device, and it comprises the film of the compound that contains general formula (I);
Fig. 4 is the schematic diagram of a multilayer device, and it comprises that one deck at least contains the film of the compound of general formula (I);
Fig. 5 is configured as ITO/PEDOT:PSS/PVK: the I-V graphic representation of the device of doping agent/TPBI/LiF/Ca/Ag, wherein said doping agent are the various compounds of general formula (I);
Fig. 6 is configured as ITO/PEDOT:PSS/PVK: the V-L graphic representation of the device of doping agent/TPBI/LiF/Ca/Ag;
Fig. 7 is the I-V graphic representation that is configured as the device of ITO/PEDOT:PSS/ compound/TPBI/LiF/Ca/Ag, and wherein said compound is the various compounds of general formula (I);
Fig. 8 is the V-L graphic representation that is configured as the device of ITO/PEDOT:PSS/ compound/TPBI/LiF/Ca/Ag;
Fig. 9 is the graphic representation of external quantum efficiency vs brightness that is configured as the device of ITO/PEDOT:PSS/ compound/TPBI/LiF/Ca/Ag;
Figure 10 is the EL spectrum that is configured as the device of ITO/PEDOT:PSS/ compound/TPBI/LiF/Ca/Ag;
Figure 11 is the UV absorption spectrum that is dissolved in the various compounds of the general formula (I) in chloroform;
The figure of the photoluminescence of the various compounds of Figure 12 measures in chloroform general formula (I);
Figure 13 is spin-coated on the figure of the photoluminescence of later these compounds in solid-state measurement on quartz plate at the chloroformic solution of the various compounds that will contain general formula (I).
Embodiment
The embodiment of the compound of the general formula (I) that the present invention describes is electroluminescent, and namely they are all luminous when electric current passes through these compounds for meaning.Therefore, these compounds all are very suitable for as the charge transport layer in organic electronic devices or luminescent layer.
Owing at molecule, comprising a large amount of π key systems, so some organic compound can conduct charges.That is to say, compound with connection or conjugatedπbond system, for example polyarylene compound (polyarylene compound) or polyarylene vinylene compound (polyarylenevinylene compound) (for example p-phenylene vinylene), a series of π molecular orbital(MO)s with overlapping and extended molecule length.When the π of these extensions molecular orbital(MO) was not filled or only is partially filled electronics, the π molecular orbital(MO) of these extensions provided passage by molecule be used to transmitting extra electronics, to pass through molecule when molecule being placed under a bias voltage.Can form the π track crossing conductive organic compound of several this extensions, each has different structures and energy level.Has the molecular orbital(MO) of lowest energy level normally be used to transmitting the effective way of extra electron.
In order to make these compound light-emittings, when by electron transport by a minute period of the day from 11 p.m. to 1 a.m, one or more electronics must be from the higher-energy rail moving of filling or being partially filled to the more low-yield track of not filling or being partially filled.If the energy that is discharged by this electronics is positioned at visible spectrum range, just can see these molecular luminescences when electronics transits to low-yield state from the high-energy state.
In brief, when being injected into hole in conductive organic molecule, this molecule can be positively charged, and on the contrary, when by in this molecule of electronic injection the time, this molecule can be electronegative.Charged molecule can obtain opposite charges from the molecule that adjoins, and causes the electric charge transmission in comprising the composition of conductive organic molecule.Institute's injected electrons and hole can be compounded to form the electrons pair that is strapped in together in luminescent layer, term is called exciton, when exciton decays to more low-yield state from excited state, can release energy.According to the wavelength that releases energy, this energy can be released to UV-light or visible light.
When with organic polymer, comparing, described compound is the molecule of less, and can after preparation, for example by column chromatography or by the crystallization process from solution, easily be purified to relatively high level, make the purity of final compound higher than polymkeric substance, and do not contain comparatively speaking unreacted initial reagent and intermediate.Therefore, in organic electronic devices, comprise these compounds and can obtain having more long lifetime and the higher device of charge transfer efficiency as charge transport layer or luminescent layer.
The compounds of this invention has electric transmission and hole transport zone simultaneously, aspect the electric charge transmission, is being therefore ambipolar.Therefore, these compounds have the charge transmission of balance, and are particularly suitable for use in thus in the organic luminescent device of OLED for example.
As shown in fig. 1, the compounds of this invention has been introduced the emission wavelength (in Fig. 1 be designated the part of A) of part to control this compound that can design and select.By Ar 7, Ar 3, Ar 2And Ar 6The part that limits can and be connected to the arbitrary substituent character on one or more described Ar groups and changes along with the number of the character of Ar group, Ar group.Each in these factors helps the emission wavelength of the specific compound of definite general formula (I).
Equally, the compound of general formula (I) has the electron-withdrawing group of one or more introducing (being designated the part of B and B ' in Fig. 1), to this compound, to provide electron transport property.Ar 6And Ar 7In at least one and one or more Ar not necessarily 2And Ar 3For electron-withdrawing group or by electron-withdrawing substituent, replace.The introducing of one or more electron-withdrawing group has strengthened electronic injection and the transmission in the luminescent layer, and this can improve the organic light-emitting device device efficiency that contains these compounds.
These compounds also have by three Ar group (Ar 1, Ar 2And Ar 3) the center tertiary N atom (this part is designated C in Fig. 1) that replaces.In being connected to three Ar groups of this center nitrogen-atoms, Ar at least 1Further to be connected on another nitrogen-atoms.This energy level that is designed with the highest occupied molecular orbital (HOMO) that helps increase this compound, the hole that is conducive to thus this compound is injected and the hole transport characteristic.Equally, this design can reduce trigger voltage and the operating voltage of the electron device of the compound that contains general formula (I).
Thus, with general formula (I), describe the compounds of this invention, it is elucidated later herein below.
In the composition of general formula (I) and in this article, " arylidene " group refers to by removing two hydrogen atoms derived from the divalence aromatic residue of aromatics.Aromatics refers to the ring compound with 4n+2 π-electron, and wherein n is equal to, or greater than 0 integer.In certain embodiments, described arylene group can have 5～100 backbone c atoms, 5～60 backbone c atoms, 5～50 backbone c atoms, 5～30 backbone c atoms or 5～20 backbone c atoms.
" aryl " group that uses in this article refers to by removing a hydrogen atom derived from the monovalent aromatic family residue of aromatics.Aromatics refers to the ring compound with 4n+2 π-electron, and wherein n is equal to, or greater than 0 integer.In certain embodiments, described aromatic yl group can have 5～100 backbone c atoms, 5～60 backbone c atoms, 5～50 backbone c atoms, 5～30 backbone c atoms or 5～20 backbone c atoms.
" heteroarylidene " group that uses in this article refers to the arylene group that one or more backbone c atoms has replaced with the heteroatoms that comprises N, O, S, Si or P.
" heteroaryl " group that uses in this article refers to the aromatic yl group that one or more backbone c atoms has replaced with the heteroatoms that comprises N, O, S, Si or P.
Should be understood that, when by specific Ar group, being described as comprising arylidene or heteroarylidene, but when this arylidene or heteroarylidene were in the end of molecule and are unit price, this special groups should be aryl or heteroaryl.For example, if by Ar 6Be described as comprising that arylidene or heteroarylidene and s are 2, so at (Ar 6) sIn end Ar 6Group will comprise aryl or heteroaryl (prerequisite is that it does not have bonding or is connected to another Ar group), but penultimate Ar 6Group will comprise arylidene or heteroarylidene.
" vinylidene " group that uses in this article refers to the residue of divalent that is represented by formula-CH=CH-.
" ethynylene " group that uses in this article refers to the residue of divalent by formula-C ≡ C-represents.
like this, the symbol " Ar " that uses in this article generally refers to aryl, arylidene, heteroaryl, heteroarylidene, aryl and the vinylidene (" aryl vinylidene ") that adjoins, arylidene and the vinylidene (" arylidene vinylidene ") that adjoins, heteroaryl and the vinylidene (" heteroaryl vinylidene ") that adjoins, heteroarylidene and the vinylidene (" heteroarylidene vinylidene ") that adjoins, aryl and the ethynylene (" aryl ethynylene ") that adjoins, arylidene and the ethynylene (" arylidene ethynylene ") that adjoins, heteroaryl and the ethynylene (" heteroaryl ethynylene ") that adjoins or heteroarylidene and the ethynylene (" heteroarylidene ethynylene ") that adjoins.
" alkyl " that use in this article refers to side chain or the unbranched univalence hydrocarbyl with 1～18 carbon atom.Similarly, " alkylidene group " that use in this article refers to side chain or the unbranched bivalent hydrocarbon radical with 1～18 carbon atom.Be to be understood that, alkenyl and alkylene group (alkenylene) are respectively to contain the unit price of one or more pair key and the term of bivalent alkyl, and alkynyl and alkynylene (alkynylene) are respectively to contain the unit price of one or more triple bond and the term of bivalent alkyl.
Therefore, one aspect of the present invention provides the compound of general formula (I):
Figure G2006800568600D00071
In above-mentioned general formula (I), Ar 1, Ar 2And Ar 3Independent separately is arylidene, heteroarylidene, arylidene vinylidene, heteroarylidene vinylidene, arylidene ethynylene or heteroarylidene ethynylene, and wherein any one can further be replaced by one or more following group: side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched heterochain thiazolinyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, aryl and heteroaryl.
Not necessarily, Ar 2And Ar 3In at least one can by one or more electron-withdrawing substituent, be replaced independently." electron-withdrawing substituent " refers to a kind of like this substituting group, and this substituting group tends to from the main chain of the group of its replacement, electronics being pulled to this substituting group, thereby on substituting group or near substituting group, producing a zone of being rich in electronics.Electron-withdrawing substituent comprises halogen, perfluoroalkyl, carbonyl, carboxyl, cyano group, ammonium, nitro, sulfinyl, alkylsulfonyl, by Sauerstoffatom, is connected to amido, pyridine, phosphorus, pyridyl, thiazolyl, oxadiazolyl and the triazolyl of main chain.
In specific embodiment, Ar 2And Ar 3In at least one comprise 9,9-dialkyl group fluorenylidene (9,9-dialkylfluorenylene).In specific embodiment, described 9,9-dialkyl group fluorenylidene is 9,9-dihexyl fluorenylidene.In other particular, Ar 2And Ar 3Each is self-contained 9,9-dialkyl group fluorenylidene.In other specific embodiment, Ar 2And Ar 3Each is self-contained 9,9-dihexyl fluorenylidene.In some specific embodiments again, Ar 2And Ar 39, the 9-dihexyl fluorenylidene of respectively doing for oneself.
In specific embodiment, Ar 1For phenylene.
Ar 4And Ar 5Independent separately is arylidene, heteroarylidene, arylidene vinylidene, heteroarylidene vinylidene, arylidene ethynylene or heteroarylidene ethynylene, and wherein any one can further be replaced by one or more following group: side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched heterochain thiazolinyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, aryl and heteroaryl.As mentioned above, at Ar 4Perhaps Ar 5In end Ar group, this end Ar group will comprise aryl or heteroaryl, rather than arylidene or heteroarylidene.
And then, Ar 1, Ar 4And Ar 5In one or more can not necessarily by one or more following group, be replaced independently: alkylthio, amino, hydroxyl, by nitrogen-atoms, be connected to amido on main chain, by Sauerstoffatom, be connected to carboxyl, phenyl, naphthyl, thienyl, furyl, pyrryl and the carbazyl on main chain.
In specific embodiment, Ar 4And Ar 5In at least one be phenyl.In other particular, Ar 4And Ar 5The phenyl of respectively doing for oneself.
And then, not necessarily, Ar 1And Ar 2, Ar 1And Ar 3, Ar 2And Ar 3, Ar 4And Ar 5, Ar 1And Ar 4And Ar 1And Ar 5In a pair of or many to can between two Ar groups, coupling together in pairs via singly-bound or via linking group, described linking group comprises O, S, Si, side chain or unbranched replacement or unsubstituted alkylidene group, side chain or unbranched replacement or unsubstituted alkylene group, side chain or unbranched replacement or unsubstituted alkynylene, as linking group.Therefore, should be understood that, for example, work as Ar 4Perhaps Ar 5While being connected to another Ar group, this specific Ar 4Or Ar 5Will be divalent group rather than monoradical.For example, if Ar 4By linking group, be connected to Ar 1, Ar 4To be for example arylidene rather than aryl.It will also be appreciated that when any one in m, n, p, r, s, x or y greater than 1 the time, between any two possible Ar groups, can produce connection.For example, if Ar 1And Ar 2Connect, and if p and n be all 2, Ar 1Any one in group can be connected to Ar 2Any one in group.Equally, Ar 1A plurality of groups in group can be connected to Ar 2One or more group in group.
In specific embodiment, Ar 4And Ar 5By singly-bound, be connected to each other.In specific embodiment, Ar 4And Ar 5Phenylene and Ar respectively do for oneself 4And Ar 5By singly-bound, be connected to each other.
Ar 6And Ar 7Independent separately is arylidene, heteroarylidene, arylidene vinylidene, heteroarylidene vinylidene, arylidene ethynylene or heteroarylidene ethynylene, and wherein any one can be replaced by one or more following group: side chain or unbranched alkyl, side chain or unbranched assorted alkyl, side chain or unbranched alkenyl, side chain or unbranched heterochain thiazolinyl, side chain or unbranched alkynyl, side chain or unbranched assorted alkynyl, side chain or unbranched alkoxyl group, aryl and heteroaryl.As mentioned above, at Ar 6Perhaps Ar 7In end Ar group, this end Ar group will comprise aryl or heteroaryl, rather than arylidene or heteroarylidene.
In addition, Ar 6And Ar 7In at least one be electrophilic Ar group and/or replaced by one or more electron-withdrawing substituent.
" electrophilic Ar group " refer to electron deficiency Ar group or the Ar group that replaces with one or more electron-withdrawing substituent to tend to along main chain from the Ar group that adjoins, accepting or attracting electronics.For example, (thiazolylene), Ya oxadiazolyl (oxadiazolylene) and inferior triazolyl (triazolylene) are all electron deficiency Ar groups for pyridylidene (pyridylene), inferior thiazolyl.Electron-withdrawing substituent comprises halogen, perfluoroalkyl, carbonyl, carboxyl, cyano group, ammonium, nitro, sulfinyl, alkylsulfonyl, by Sauerstoffatom, is connected to amido, pyridine, phosphorus, pyridyl, thiazolyl, oxadiazolyl and the triazolyl of main chain.
Electrophilic Ar group often makes electrophilic Ar group have higher electron density than non-electrophilic contiguous Ar group from the contiguous electrophilic ability of Ar group, is similar to the n-shaped material that uses in silicon semiconductor, and thus more can transmission electronic.Usually, electron-withdrawing group is such group, and its zone at contiguous main chain produces positive region or δ positive region with from main chain, electronics being pulled to substituting group.
In certain embodiments, Ar 6Or Ar 7In at least one by one or more electron-withdrawing substituent, replaced, wherein electron-withdrawing substituent comprises halogen, perfluoroalkyl, carbonyl, carboxyl, cyano group, ammonium, nitro, sulfinyl, alkylsulfonyl, by Sauerstoffatom, is connected to amido, pyridine, phosphorus, pyridyl, thiazolyl, oxadiazolyl and the triazolyl of main chain.
In certain embodiments, Ar 6Or Ar 7In at least one be one or more following Ar group; wherein R, R ', R " and R " ' separately are independently halogen, cyano group, nitro, carbonyl, sulfinyl, alkylsulfonyl, alkyl, perfluoroalkyl, alkoxyl group, aryl, arylidene vinylidene or arylidene ethynylene, and q is 0～6 integer.
Should be understood that, although the Ar group below some is depicted as to unit price or divalence, as mentioned above, according to this Ar group residing position in compound, any group can or unit price or divalence.Equally, some compound is depicted as to the key with the remainder of this group of connection of the form to enter this Ar group Huan De center and compound, or on atom or pass through key.Should be understood that, this describing is intended to represent that this specific Ar group can be connected to by the key of any one available position on this ring the remainder of this compound.
M, n, p, r, s, x and y are independently 1～20 integer separately.Same, should be understood that, m, n, p, r, s, x and y can be arbitrary numerical value between 1～20 and any scope in 1～20 separately, for example, 1～15,1～10 or 1～5 or 10～15 or 10～20.If any one in m, n, p, r, s, x or y be greater than 1, for relevant Ar group (for example, for the Ar of r 7) each appearance, the selection of this Ar group is all independently.For example, when r is 5,5 Ar 7The selection of each in group is independent of remaining 4 Ar 7Group.
In specific embodiment, Ar 6And Ar 7In at least one be phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9,9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl or 7-(4 '-cyano-phenyl)-9,9-dihexyl fluorenyl.In specific embodiment, Ar 6And Ar 7Identical, and be as phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9 9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl or 7-(4 '-cyano-phenyl)-9,9-dihexyl fluorenyl.
In specific embodiment, Ar 1For phenylene, Ar 2And Ar 3Be 9,9-dihexyl fluorenylidene, Ar 4And Ar 5Be phenylene and be connected with each other by singly-bound, Ar 6And Ar 7Identical and be phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9,9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl or 7-(4 '-cyano-phenyl)-9,9-dihexyl fluorenyl, and m, n, p, r, s, x and y respectively do for oneself 1.
The compound of general formula (I) can use the standard organic synthesis technology that is known in the art synthetic.The Examples set of the synthesis mechanism that is suitable for is in the embodiment that Fig. 2 neutralization is elucidated later herein below.For example can use ullmann reaction (Ullmann reaction) to come coupling aromatic halides and arylamine.Equally, can use Grignard reaction (Grignard reaction), Si Dier reaction (Stille reaction) to be connected two aromatic series functional groups with Suzuki coupled reaction (Suzuki coupling reaction).
As mentioned above, the compound of general formula (I) can carry out purifying by for example column chromatography or by the standard method from crystallization solution.These technology are known, and those of skill in the art make great efforts just can easily these technology be applied to the compound of general formula (I) by the routine of minimum.
The compound of describing in this article is applicable to solution processing, makes thus and can produce the film that contains these compounds.Therefore, one aspect of the present invention provides the film of the compound that contains general formula (1).
Described film is for containing the thin layer of compound of general formula (1), the thickness of its formation can be followed successively by approximately to 0.1～about 1000nm, approximately 1～about 500nm, approximately 5～about 250nm or about 5～about 100nm.
Described film can contain other composition.For example, this film can comprise for example material of main part of conductive organic compound and the compound of general formula (I).this material of main part can be: for example gather (9-vinylcarbazole) (PVK), 4,4 '-N, N '-bis-carbazoles-biphenyl (CBP), 4,4 ', 4 "-tri-(N-carbazole) triphenylamines (TCTA), N, N '-phenylbenzene-N, N '-bis-(3-aminomethyl phenyl) (1,1 '-phenylbenzene)-4,4 '-diamines (TPD), N, N '-bis-(1-naphthyl)-N, N '-phenylbenzene-1,1 "-phenylbenzene-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(N, N-phenylbenzene-amino) triphenylamines (TDATA), 1,3,5-tri-(diphenyl amino) benzene (TDAB), 1,3,5-tri-(4-(two-2-pyridinylamino) phenyl) benzene (TDAPB), TTBND, PPD, PTDATA, BFA-1T, p-dmDPS, p-DPA-TDAB, MTBDAB, spiral shell-mTTB, DBC, the p-phenylene vinylene, poly-fluorenes, polystyrolsulfon acid, poly-(3,4-Ethylenedioxy Thiophene) (poly (3,4-ethylenedioxythiophene)), polyacetylene, polypyrrole, polyaniline, 3-phenyl-4 (1 ' naphthyl)-5-phenyl-1,2,4-triazole (TAZ), 2-(4-phenylbenzene)-5 (the 4-tertiary butyl-phenyl)-1,3,4-oxadiazole (PBD), 2,2 '-(1,3-phenylene) two [5-[4-(1,1-dimethyl ethyl) phenyl]]-1,3,4-oxadiazole (OXD-7) or poly-[2-(6-cyano group-6-methyl) Oxy-1 in heptan, 4-phenylene] are (CNPP), AlOq, Alq (Clq) 2, Al (Saph-q), Al (ODZ) 3, Ph 2Bq, Zn (BIZ) 2, Bepp 2, Bebq 2, Zn (ODZ) 2, spiral shell-PBD, BMB-3T.
The ratio of the compound of material of main part and general formula (I) can be approximately 100: 0.01～approximately 0.01: 100.
in addition, the compound that described film can contain general formula (I) is as material of main part and can further contain organic dye or phosphorescent emitters, for example, dyestuff is such as 10-(2-[4-morpholinodithio base)-1, 1, 7, 7-tetramethyl--2, 3, 6, 7-tetrahydrochysene-1H, 5H, 11H-[l] chromene also [6, 7, 8-ij] quinolizine-11-ketone (10-(2-benzothiazolyl)-1, 1, 7, 7-tetramethyl-2, 3, 6, 7-tetrahydro-1H, 5H, 11H-[l] benzo-pyrano[6, 7, 8-ij] quinolizin-11-one), 3-(2-[4-morpholinodithio base)-7-(diethylin)-2H-1-chromen-2-one, 4-(the dicyano methylene)-2-tertiary butyl-6-(1, 1, 7, 7-tetramethyl-julolidine-9-thiazolinyl)-4H-pyrans (4-(dicyanomethylene)-2-t-butyl-6-(1, 1, 7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran) (DCJTB), rubrene, 4-(the dicyano methylene)-2-tertiary butyl-6-(to the diphenyl amino styryl)-4H-pyrans (4-(dicyanomethylene)-2-t-butyl-6-(p-diphenylaminostyryl)-4H-pyran) (DCTP), 3-(dicyano methylene)-5, 5-dimethyl-1-[(4-dimethylamino) styryl] tetrahydrobenzene (3-(dicyanomethylene)-5, 5-dimethyl-1-[(4-dimethylamino) styryl] cyclohexene) (DCDDC), 6-methyl-3-[3-(1, 1, 6, 6-tetramethyl--10-oxo-2, 3, 5, 6-tetrahydrochysene-1H, 4H, 10H-11-oxa--3a-azepine benzo [de]-anthracene-9-yl) acryl] pyrans-2, (6-methyl-3-[3-(1 for the 4-diketone, 1, 6, 6-tetramethyl-10-oxo-2, 3, 5, 6-tetrahydro-1H, 4H, 10H-11-oxa-3a-azabenzo[de]-anthracen-9-yl) acryloyl] pyran-2, 4-dione) (AAAP), 6, (N-is to the amino) perylene [(PPA) (PSA) Pe-1] of styryl phenyl-N-p-methylphenyl for 13-phenylbenzene pentacene (DPP) and 3-(N-phenyl-N-p-methylphenyl amino)-9-, 1, the bisstyryl naphthalene derivatives (1 that 1 '-dicyano replaces, 1 '-dicyano-substituted bis-styrylnaphthalene derivative) (BSN), perhaps phosphorescent emitters is such as PtOEP, Ir (ppy) 3or derivatives thereof.
Compound disclosed in this invention is approximately 100: 0.01～approximately 1: 1 with the ratio of described dyestuff or phosphorescent emitters.
Described film can be formed on suitable substrate, and this substrate can be any solid substrate, comprising: the plastic base of quartz, glass, mica, for example polyethylene terephthalate or polycarbonate, paper, metal or silicon.This film also can be laminated in above another layer or above electrode when forming multilayer device.
In order to form described film, the compound of general formula (I) and any other film component can be dissolved in suitable organic solvent.The solvent that is suitable for comprises: the mixture of chloroform, toluene, dimethylbenzene, ethyl benzoate, sym.-tetrachloroethane, THF, dichlorobenzene, 1，3，5-trimethyl-benzene and above-mentioned solvent.
Can the Application standard sedimentation or comprise that the coating process of solution coat method is formed on described film on suitable surface.The solution coat method comprises spin-coating method, teeming practice, nick version coating method, intaglio plate coating method, excellent painting method, rolling method, coiling rod coating method, dip coating, spraying method, silk screen print method, flexographic printing method, offset printing method and ink jet printing method.
The compound of general formula (I) can be used for building electroluminescent device with the film that contains this compound, comprises individual layer and multilayer device.The compound of general formula (I) can be formed with the luminescent layer in OLED, the active coating of OTFT or the active coating in organic photovoltaic battery with the film that contains this compound.These devices and layer are known in the art.
Therefore, another aspect of the present invention provides the device of the compound that comprises general formula (I) or has comprised the device of the film of the compound that comprises general formula (I).
In one embodiment, with reference to figure 3, device 300 comprises the luminescent layer 310 of the compound that comprises general formula (I).As mentioned above, luminescent layer 310 can further comprise the material of main part except the compound of general formula (I).
Luminescent layer 310 is arranged on electronic injection negative electrode 320 and hole is injected between anode 330.
Anode 330 is can transporting holes and be injected into any material in organic layer.Anode 330 can be gold and silver or tin indium oxide (ITO), or conductive polymer coating.Anode 330 can be reflection, transparent or translucent (semi-transparent, translucent).
Negative electrode 320 is can transmission electronic and be injected into any material in organic layer.Negative electrode 320 can be low workfunction metal or metal alloy, comprise: for example, barium, calcium, magnesium, indium, aluminium, ytterbium, calcium silver alloys, Al-Li alloy or magnesium silver alloys, for example, wherein magnesium is about the alloy (US 6,791,129) of 10: 1 with the atomic ratio of silver, perhaps wherein the atomic ratio of lithium and aluminium is alloy (people such as Kim, (2002) Curr.Appl.Phys.2 (4): 335-338 of approximately 0.1: 100～approximately 0.3: 100; The people such as Cha, (2004) Synth.Met.143 (1): 97; The people such as Kim, (2004) Synth.Met.145 (2-3): 229).Negative electrode 330 can be individual layer or have composite structure.Negative electrode 330 can comprise lithium fluoride layer, aluminium lamination and silver layer.Negative electrode 330 can be reflection, transparent or translucent.
In certain embodiments, one or more anode and negative electrode can be deposited on supporter 340, and it can be transparent or translucent.Supporter 340 can be rigidity, for example quartz or glass, or can be flexible polymer substrate.The example of flexible and transparent or translucent substrate comprises, but be not limited to, the fluorinated polymer of polyimide, tetrafluoroethylene, polyethylene terephthalate, for example polypropylene and poly polyolefine, polymeric amide, polyacrylonitrile (polyacrylonitrile, polyacrionitrile), polymethacrylonitrile, polystyrene, polyvinyl chloride and for example tetrafluoroethylene.
This device may further include other layer.In one embodiment, as shown in Figure 4, device 400 is an Organic Light Emitting Diode (OLED).
Therefore, device 400, except luminescent layer 410, also comprise anode 420 and negative electrode 430.
Device 400 also comprises the hole transmission layer 440 that is arranged between anode 420 and luminescent layer 410.Hole transmission layer 440 comprises hole mobile material, and this hole mobile material is for importing hole into luminescent layer 410 any material from anode 420.The hole mobile material that is suitable for comprises for example mixture of poly-(3,4-Ethylenedioxy Thiophene) and poly-(styrene sulfonic acid), or can be polyaniline.
Not necessarily, between anode 420 and hole transmission layer 440, can comprise hole injection layer 480.hole injection layer 480 comprises hole-injecting material, for example 4, 4 '-N, N '-bis-carbazoles-biphenyl (CBP), 4, 4 ', 4 "-tri-(N-carbazole) triphenylamines (TCTA), N, N '-phenylbenzene-N, N '-bis-(3-aminomethyl phenyl) (1, 1 '-phenylbenzene)-4, 4 '-diamines (TPD), N, N '-bis-(1-naphthyl)-N, N '-phenylbenzene-1, 1 "-phenylbenzene-4, 4 '-diamines (NPB), TDATA, TDAB, TDAPB, TTBND, PPD, PTDATA, BFA-1T, p-dmDPS, p-DPA-TDAB, MTBDAB, spiral shell-mTTB, DBC, p-phenylene vinylene's or derivatives thereof, perhaps gather the fluorenes or derivatives thereof.
Device 400 can not necessarily comprise the electron transfer layer 450 that is arranged between luminescent layer 410 and negative electrode 430.Electron transfer layer 450 comprises electron transport material, and this electron transport material is for can transfer to electronics any material of luminescent layer 410 from negative electrode 430.electron transport material is known to those skilled in the art, and comprise three (oxine) aluminium, 2-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazole and 2, 2 ', 2 "-(1, 3, 5-benzene three bases) three-[1-phenyl-1H-benzoglyoxaline], 3-phenyl-4 (1 ' naphthyl)-5-phenyl-1, 2, 4-triazole (TAZ), 2, 2 '-(1, the 3-phenylene) two [5-[4-(1, the 1-dimethyl ethyl) phenyl]]-1, 3, 4-oxadiazole (OXD-7) or poly-[2-(6-cyano group-6-methyl) Oxy-1 in heptan, the 4-phenylene] (CNPP), AlOq, Alq (Clq) 2, Al (Saph-q), Al (ODZ) 3, Ph2Bq, Zn (BIZ) 2, Bepp2, Bebq2, Zn (ODZ) 2, spiral shell-PBD or BMB-3T.
The thickness of above-mentioned each layer can be, for example, and about 0.1nm～about 200nm or about 10nm～about 100nm.
Device 400 can not necessarily be included in the hole blocking layer 460 between luminescent layer 410 and negative electrode 430.Particularly, if be present in device 400, hole blocking layer 460 is arranged between electron transfer layer 450 and negative electrode 430.
Usually, the efficiency of OLED device can increase by introducing hole blocking layer.Be not subject to any particular theory, the HOMO energy level that it is believed that hole barrier materials prevents that electric charge from spreading out from luminescent layer, but hole barrier materials has enough low ELECTRONIC COVER, allow electronics by hole blocking layer and enter luminescent layer (for example referring to US 6,097,147, US 6,784,106 and US20030230980).
Hole blocking layer 460 comprises hole barrier materials.Hole barrier materials is known for those of skill in the art, and comprises: for example, and 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) (BCP) and 1,3,5-tri-(phenyl-2-benzimidazolyl-) benzene (1,3,5-tris (phenyl-2-benzimidazolyl) benzene) (TPBI).Generally speaking, hole blocking layer 460 is thinner than electron transfer layer 450, and has for example thickness of about 5nm～about 30nm.
Device 400 can not necessarily comprise and is adjacent to the electron injecting layer 470 that arranges before negative electrode 430.Electron injecting layer 470 comprises electron injection material, and electron injection material is any material of 450 transmission electronics from negative electrode 430 to electron transfer layer effectively.Electron injection material is known for those of skill in the art, and comprises, for example lithium fluoride or lithium fluoride/aluminium.The thickness of electron injecting layer 470 is usually much smaller than 450 thickness of the thickness of negative electrode 430 or the electron transfer layer that adjoins, and can be, for example about 0.5nm～about 5.0nm.
As device 300, device 400 can deposit or be formed on supporter.
Should be understood that, can prepare by making up in a different manner different layers by this device, and other layer that does not specifically describe in device 400 or describe is also passable.
Equally, should be understood that, a kind of material may provide more than one function in electroluminescent device.Due to the bipolarity charge-transporting matter of the compound of general formula (I), so these compounds can be used in other layer of above-mentioned device.For example, the compound of general formula (I) can be separately or is formed hole transmission layer or electron transfer layer as the part of mixture.
Therefore, the device of describing at present comprises such device, and wherein the one deck at least in hole transmission layer, luminescent layer, hole blocking layer and electron transfer layer comprises the compound of general formula (I).
Above-mentioned device can be by being laminated in relevant layers top preparation the one by one.These layers can be used in method preparation as known in the art, comprise above-mentioned solution coat technology.The solution coat step can for example carried out under the inert atmosphere in nitrogen.In addition, can prepare these layers by hot vapour deposition method or by vacuum deposition method.Can prepare metal level by known technology, for example heat or electron beam evaporation plating, chemical vapour deposition or sputter.
Embodiment
Instrument: nucleus magnetic resonance (NMR) spectrum is measured with Bruker DPX 400MHz spectrograph, use chloroform-d as solvent and tetramethylsilane (TMS) as interior mark.Substance assistant laser desorpted/ionization flight time (MALDI-TOF) mass spectrum uses Bruker Autoflex TOF/TOF instrument to carry out.High performance liquid chromatography (HPLC) uses Waters 2695 separation modules that are combined with Waters 2996 photodiode array detectors to carry out.Dsc (DSC) under nitrogen, use TAInstrument DSC 2920 modules carry out (sweep velocity be 20 ℃/min).Thermogravimetric analysis (TGA) uses TA Instrument TGA 2050 modules to carry out (rate of heating: 20 ℃/min).Autolab potentiostat (model: PGSTAT30) carry out is used in cyclic voltammetric (CV) experiment.All CV measures and to carry out (sweep velocity: 50mV/s) in as the methylene dichloride of supporting electrolyte containing 0.1M tetrabutyl ammonium hexafluorophosphate, use three conventional electrode configurations, by platinum filament working electrode, gold, electrode and the Ag/AgCl reference electrode in 3MKCl are formed.According to general-4.4eV as the SCE energy level with respect to vacuum, measured current potential is converted into to SCE (saturated calomel electrode) current potential and corresponding ionization potential (IP), and derives electron affinity (EA) (EA=E from initial oxidation reduction potential (onset redox potential) Initial reduction+ 4.4eV (EA=Ered-onset+4.4eV), IP=E Initial oxidation+ 4.4eV (IP=Eox-onset+4.4eV)).Use is with Shimadzu UV-3101PC ultraviolet-visible-near infrared spectrometer and Perkin-Elmer LS-50B fluorescence spectrophotometer measurement absorption spectrum and the photoluminescence spectra of xenon lamp as light source.Solution spectrum is from measuring dichloromethane solution.
Synthetic: the synthetic method that the following describes is depicted in the synthetic schematic diagram shown in Fig. 2.
Synthesizing of 9-(4-bromophenyl) carbazole (9-(4-bromophenyl) carbazole): according to (Macromolecules 2004 at document, 37,5531-5537) method of middle report prepares 9-(4-bromophenyl) carbazole by ullmann reaction.In brief, will be at 10mlN, the bromo-4-iodobenzene of 1-(2.83g, 10mmol) in N-N,N-DIMETHYLACETAMIDE (DMAC), Red copper oxide (copper (I) oxide) (2.86g, 20mmol) and the mixture of carbazole (0.84g, 5mmol) at N 2Under atmosphere in oil bath reflux 24h.Reaction mixture is cooled to room temperature, then filters and remove excessive copper complex.Filtrate is evaporated to dried, and obtains the 1.22g product through silicagel column, productive rate 76%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.132-8.122(d，J＝8.0Hz，2H)，7.715-7.695(t，J＝8.0Hz，2H)，7.476-7.247(m，8H)。
(2-bromo-9 for 4-, 9-dihexyl-9H-fluorenes-7-yl) benzonitrile (4-(2-bromo-9,9-dihexyl-9H-fluoren-7-yl) benzonitrile) synthetic: prepare as follows 4-(2-bromo-9,9-dihexyl-9H-fluorenes-7-yl) benzonitrile.By 2,7-bis-bromo-9,9-dihexyl-9H-fluorenes (2,7-dibromo-9,9-dihexyl-9H-fluorene) (0.985g, 2mmol), the mixture of 4-cyano-phenyl boric acid (4-cyanophenylboronicacid) (0.146g, 1mmol) and tetrakis triphenylphosphine palladium (tetrakis (triphenylphosphine) palladium) (11.6mg, 0.01mmol) joins airfree toluene (25mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (15mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain the 0.27g pure products, productive rate 51%. 1HNMR(400MHz，CDCl 3)：δ(ppm)7.766-7.751(m，5H)，7.605-7.583(d，J＝8.8Hz，1H)，7.583-7.564(d，J＝7.6Hz，1H)，7.524(s，1H)，7.495-7.476(m，2H)，2.013-1.964(m，4H)，1.140-1.053(m，12H)，0.781-0.746(t，J＝7.0Hz，6H)，0.658-0.624(m，4H)。
(A) synthetic of 4-(9H-carbazole-9-yl) aniline (4-(9H-carbazol-9-yl) benzenamine): according to (Macromolecules 2004 at document, 37,5531-5537) method of middle report prepares 4-(9H-carbazole-9-yl) aniline (A) by ullmann reaction.By the mixture of 4-Iodoaniline (2.19g, 10mmol), Red copper oxide (2.18g, 20mmol) and carbazole (3.35g, 20mmol) in 40ml 1-phenyl ether (1-phenoxybenzene) at N 2Under atmosphere, in oil bath, be heated to 190 ℃ of reaction 24h.Reaction mixture is cooled to room temperature, then with quick silicagel column, filters to remove excessive copper complex and 1-phenyl ether.Filtrate is evaporated to dried, and uses the mixture (6: 1) of hexane and ethyl acetate as elutriant, by silicagel column, to obtain the 2.37g product, productive rate 92%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.164-8.144(d，J＝8.0Hz，2H)，7.432-7.395(t，J＝8.0Hz，2H)，7.353-7.277(m，6H)，6.912-6.891(d，J＝7.6Hz，2H)，4.019(w，2H)。
Synthesizing of compound (B): prepare compound (B) according to top step.2-in the 1-phenyl ether is bromo-9, the iodo-9H-fluorenes of 9-dihexyl-7-(17.26g, 32mmol), Red copper oxide (2.29g, 16mmol) and (A) mixture of (2.07g, 8mmol) at N 2Under atmosphere, in oil bath, be heated to 210 ℃ of reaction 24h.Reaction mixture is cooled to room temperature, then filters and remove excessive copper complex.Filtrate is evaporated to dried, and obtains the 4.35g product through silicagel column, productive rate 50%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.190-8.171(d，J＝7.7Hz，2H)，7.625-7.605(d，J＝8.0Hz，2H)，7.531-7.440(m，12H)，7.351-7.263(m，6H)，7.175-7.157(d，J＝ 7.6Hz，2H)，1.936-1.898(m，8H)，1.174-1.109(m，24H)，0.810-0.776(t，J＝7.2Hz，12H)，0.726(m，8H)。
Synthesizing of compound (C): prepare according to the following steps compound (C).In anhydrous THF (40mL) solution of (B) (2.16g, 2mmol) at-78 ℃, add n-Butyl Lithium (1.6M is in hexane for 5mL, 8mmol).Mixture stirs 1h at-78 ℃.In this solution, add fast 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-dioxane pentaborane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2.4mL, 12mmol).Mixture is heated to room temperature and stirs and spend the night.Then pour into this mixture in water and use extracted with diethyl ether.Merge organic extract liquid, with the salt water washing, also use anhydrous MgSO 4Dry.Solution is removed in decompression, and obtains the 1.36g product, productive rate 58% by the recrystallization purifying crude product from the hexane/chloroform mixture. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.186-8.166(d，J＝8.0Hz，2H)，7.620-7.601(d，J＝7.6Hz，2H)，7.505-7.435(m，12H)，7.334-7.257(m，6H)，7.168-7.149(d，J＝7.6Hz，2H)，1.930-1.893(m，8H)，1.589(s，24H)，1.168-1.104(m，24H)，0.804-0.770(t，J＝7.2Hz，12H)，0.722(m，8H)。
Synthesizing of compound 1: the mixture of (B) (0.162g, 0.15mmol), phenyl-boron dihydroxide (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) is joined to airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.134g pure compound 1, productive rate 83%. 1HNMR(400MHz，CDCl 3)：δ(ppm)8.154(d，2H)，7.675(m，8H)，7.578(m，6H)，7.479(m，10H)，7.358(m，4H)，7.251(m，4H)，1.977(m，8H)，1.092(m，24H)，0.763(m，20H)。MS (MALDI): m/z=1074.79 is (to C 80H 86N 2Calculated value: 1074.68).Analyze and find: C, 89.03; H, 8.05; N, 2.73 (calculated value: C, 89.34; H, 8.06; N, 2.60).
Synthesizing of compound 2: by (B) (0.162g, 0.15mmol), the mixture of trifluoromethyl phenyl boronic acid (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.115g pure compound 2, productive rate 63%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.163(d，2H)，7.769(m，6H)，7.734(m，6H)，7.759(d，2H)，7.548(m，2H)，7.453(m，6H)，7.307(m，6H)，7.197(m，2H)，1.977(m，8H)，1.106(m，24H)，0.768(m，20H)。MS (MALDI): m/z=1210.77 is (to C 82H 84F 6N 2Calculated value: 1210.65).Analyze and find: C, 81.32; H, 6.81; N, 2.29 (calculated value: C, 81.29; H, 6.99; N, 2.31).
Synthesizing of compound 3: by (B) (0.162g, 0.15mmol), the mixture of 2-naphthyl boric acid (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.104g pure compound 3, productive rate 59%. 1HNMR(400MHz，CDCl 3)：δ(ppm)8.177(d，2H)，8.124(m，2H)，7.947(m，6H)，7.900(d，2H)，7.853(d，2H)，7.732(m，8H)，7.511(m，12H)，7.323(m，4H)，2.041(m，8H)，1.127(m，24H)，0.776(m，20H)。MS (MALDI): m/z=1174.83 is (to C 88H 90N 2Calculated value: 1174.71).Analyze and find: C, 89.58; H, 7.31; N, 2.38 (calculated value: C, 89.90; H, 7.72; N, 2.38).
Synthesizing of compound 4: by (B) (0.162g, 0.15mmol), the mixture of 3-thionaphthene ylboronic acid (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.98g pure compound 4, productive rate 55%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.174-8.155(d，J＝7.6Hz，2H)，7.858-7.838(d，J＝8.0Hz，2H)，7.801-7.782(d，J＝7.6Hz，2H)，7.704-7.617(m，10H)，7.489-7.450(m，6H)，7.367-7.274(m，10H)，7.220(w，2H)，1.987(m，8H)，1.111(m，24H)，0.782-0.749(m，20H)。 13CNMR(400MHz，CDCl3)：δ(ppm)141.496，141.290，139.818，126.222，124.905，124.585，123.781，122.581，120.668，120.241，110.212，55.706，40.700，31.938，30.057，24.330，22.892，14.323。MS (MALDI): m/z=1186.76 is (to C 84H 86N 2S 2Calculated value: 1186.62).Analyze and find: C, 84.86; H, 7.46; N, 2.45; S, 5.25 (calculated value: C, 84.94; H, 7.30; N, 2.36; S, 5.40).
Synthesizing of compound 5: the mixture of (C) (0.176g, 0.15mmol), 9-bromine luxuriant and rich with fragrance (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) is joined to airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.129g pure compound 5, productive rate 67%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.804(d，2H)，8.746(d，2H)，8.162(d，2H)，8.798(d，2H)，7.934(d，2H)，7.780(m，4H)，7.695(m，8H)，7.526(m，8H)，7.458(m，6H)，7.248(m，6H)，1.979(m，8H)，1.147(m，24H)，0.866(m，8H)，0.793(m，12H)。MS (MALDI): m/z=1274.89 is (to C 96H 94N 2Calculated value: 1274.74).Analyze and find: C, 90.54; H, 7.21; N, 2.21 (calculated value: C, 90.38; H, 7.43; N, 2.20).
Synthesizing of compound 6: by (C) (0.176g, 0.15mmol), 2-bromo-9, the mixture of 9-dihexyl fluorenes (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.157g pure compound 6, productive rate 66%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.177(d，2H)，7.794(d，2H)，7.750(d，4H)，7.664(m，6H)，7.621(m，4H)，7.453(m，8H)，7.362(m，6H)，7.335(m，6H)，2.036(m，18H)，1.126(m，48H)，0.771(m，40H)。MS (MALDI): m/z=1587.28 is (to C 118H 142N 2Calculated value: 1587.12).Analyze and find: C, 89.43; H, 8.69; N, 1.78 (calculated value: C, 89.23; H, 9.01; N, 1.76).
Synthesizing of compound 7: the mixture of (C) (0.176g, 0.15mmol), 1-bromine pyrene (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) is joined to airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.108g pure compound 7, productive rate 54%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.271(d，2H)，8.260(d，2H)，8.206(d，2H)，8.182(m，2H)，8.170(d，2H)，8.121(m，4H)，8.099(d，2H)，8.046(s， 2)，8.023(m，2H)，7.845(m，2H)，7.758(d，2H)，7.612(m，4H)，7.513(m，2H)，7.460(m，6H)，7.381(m，2H)，7.308(m，4H)，2.005(m，8H)，1.169(m，24H)，0.905(m，8H)，0.806(t，12H)。MS (MALDI): m/z=1323.92 is (to C 100H 94N 2Calculated value: 1323.74).Analyze and find: C, 90.65; H, 7.02; N, 2.13 (calculated value: C, 90.73; H, 7.16; N, 2.12).
Synthesizing of compound 8: by (C) (0.176g, 0.15mmol), the mixture of 9-(4-bromophenyl) carbazole (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.118g pure compound 8, productive rate 56%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.184(d，6H)，7.907(m，4H)，7.692(m，10H)，7.516-7.425(m，18H)，7.315(t，10H)，2.022(m，8H)，1.134(m，24H)，0.785(m，20H)。MS (MALDI): m/z=1404.96 is (to C 104H 100N 4Calculated value: 1404.79).Analyze and find: C, 88.74; H, 7.01; N, 3.98 (calculated value: C, 88.85; H, 7.17; N, 3.98).
Synthesizing of compound 9: by (B) (0.162g, 0.15mmol), the mixture of 4-cyano-phenyl boric acid (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.147g pure compound 9, productive rate 87%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.172(d，2H)，7.758(m，10H)，7.683(d，2H)，7.592(d，2H)，7.534(s，2H)，7.460(m，6H)，7.366(m，2H)，7.301(m，4H)，7.198(m，2H)，1.980(m，8H)，1.095(m，24H)，0.756(m，20H)。MS (MALDI): m/z=1124.76 is (to C 82H 84N 4Calculated value: 1124.67).Analyze and find: C, 87.34; H, 7.33; N, 5.06 (calculated value: C, 87.50; H, 7.52; N, 4.98).
Synthesizing of compound 10: by (C) (0.176g, 0.15mmol), the bromo-7-of 2-(4 '-cyano-phenyl)-9, the mixture of 9-dihexyl fluorenes (0.6mmol) and tetrakis triphenylphosphine palladium (3.4mg, 0.003mmol) joins airfree toluene (15mL) and 2M Na 2CO 3In the two-phase mixture of the aqueous solution (12mL).Under argon gas atmosphere by resulting mixture 110 ℃ of vigorous stirring 24 hours.Separate organic layer and use ether extraction water solution phase.Organic layer salt water washing (2x50mL), and use anhydrous MgSO 4Dry.Evaporating solvent also passes through silicagel column by resistates.By recrystallization in heptane, obtain 0.160g pure compound 10, productive rate 60%. 1H NMR(400MHz，CDCl 3)：δ(ppm)8.183-8.163(d，J＝8.0Hz，2H)，7.843-7.824(d，J＝7.6Hz，4H)，7.777-7.745(m，10H)，7.707-7.582(m，14H)，7.527-7.506(d，J＝8.4Hz，2H)，7.460-7.447(m，4H)，7.396-7.376(d，J＝8.0Hz，2H)，7.343-7.293(m，4H)，7.231-7.210(d，J＝8.4Hz，2H)，2.106(m，16H)，1.141(m，48H)，0.800-0.755(m，40H)。 13C NMR(400MHz，CDCl3)：δ(ppm)153.075，152.502，152.279，151.876，147.906，147.266，146.589，142.027，141.578，140.618，140.239，139.780，138.230，136.934，132.958，131.715，128.102，126.675，126.237，124.306，123.866，121.962，121.049，120.668，120.199，119.994，119.878，119.356，111.088，110.197，55.852，55.708，40.716，31.947，31.809，30.063，24.364，24.237，22.884，14.339。MS (MALDI): m/z=1789.42 is (to C 132H 148N 4Calculated value: 1789.17).Analyze and find: C, 88.62; H, 8.25; N, 3.14 (calculated value: C, 88.54; H, 8.33; N, 3.13).
Prepared by device and according to following configuration, prepared by measurement and estimated the device of two types.
Configuration A (ITO/PEDOT:PSS/PVK: doping agent/TPBI/LiF/Ca/Ag): the relevant light-emitting dopant of 1.2mg (compound of synthetic general formula (I) as mentioned above) and 60mg poly-(9-vinylcarbazole) (PVK) are dissolved in the ethyl benzoate of 4ml and the PTFE strainer filtration by 0.2mm for the preparation of device.
Prepared on the glass substrate that applies with tin indium oxide (ITO) of patterning by luminescent device.Clean and with this substrate of oxygen plasma treatment, what the use that spin coating 50nm is thick on this substrate poly-(styrene sulfonic acid) (PSS) adulterate gathers (3,4-Ethylenedioxy Thiophene) (PEDOT), subsequently in air 120 ℃ of dryings 15 minutes.
This polymers soln spin coating is formed to thickness to be about the luminescent layer of 70nm and to change 1 * 10 over to -5In the vacuum chamber of Pa.By 40nm thick 1,3,5-tri-(phenyl-2-benzoglyoxaline) benzene (TPBI) is deposited on the surface of this luminescent layer for electronic injection and hole barrier.
Negative electrode is comprised of 0.4nm LiF, 20nm Ca and the 200nm Ag of order heat deposition.
All measurements are all at room temperature carried out in air.The photorectifier that uses Keithley 2420 source tables and calibrated is measured current-voltage, the electric current-light characteristic of these devices.Use Ocean Optics USB2000 micro fiber spectrometer to measure EL spectrum.Use current-voltage-brightness data and the EL spectrum of these devices to calculate the photometric measurement data.
The device performance that contains the device of compound 1～10 is summarised in table 1.Fig. 5 and 6 is I-V and V-L curves of the device of configuration A.Table 1. has the summary of device performance of the compound 1～10 of device configuration A
Compound Trigger voltage (V) At 100cd/m 2Voltage (V) Maximum current efficiency (cd/A) Maximum external quantum efficiency (%) λ max EL(nm) CIE (x，y)
1 5.4 9.4 1.25 2.12 426 0.160，0.085
2 6.2 10.4 1.19 1.20 440 0.180，0.131
3 5.5 9.0 1.21 1.84 434 0.155，0.089
4 5.6 9.9 1.55 1.93 442 0.151，0.106
5 6.4 11.0 0.73 0.99 433 0.157，0.099
6 5.9 10.0 1.71 1.64 432 0.205，0.158
7 5.9 9.9 1.57 1.97 440 0.150，0.108
8 6.1 9.8 0.99 1.18 436 0.163，0.110
9 5.1 8.5 2.49 2.30 448 0.152，0.148
10 5.3 9.6 3.50 3.40 446 0.178，0.160
Configuration B (the ITO/PEDOT:PSS/ light emitting molecule/TPBI/LiF/Ca/Ag):
The synthetic light emitting molecule as mentioned above of 60mg is dissolved in the ethyl benzoate of 4ml and the PTFE strainer by 0.2mm filters for the preparation of device.
Prepared on the glass substrate that applies with tin indium oxide (ITO) of patterning by luminescent device.Clean and with this substrate of oxygen plasma treatment, what the use that spin coating 50nm is thick on this substrate poly-(styrene sulfonic acid) (PSS) adulterate gathers (3,4-Ethylenedioxy Thiophene) (PEDOT), subsequently in air 120 ℃ of dryings 15 minutes.
The spin coating of light emitting molecule solution is formed to thickness to be about the luminescent layer of 70nm and to change 1 * 10 over to -5In the vacuum chamber of Pa.By 40nm thick 1,3,5-tri-(phenyl-2-benzoglyoxaline) benzene (TPBI) is deposited on the surface of this luminescent layer for electronic injection and hole barrier.
Negative electrode is comprised of 0.4nm LiF, 20nm Ca and the 200nm Ag of order heat deposition.
The device performance that contains the device of compound 1～10 is summarised in table 2.Fig. 7 and 8 is I-V and V-L curves of the device of configuration B.Fig. 9 is the EL spectrum that the curve of outside quantum effect vs brightness of configuration B and Figure 10 have described to have the device of configuration B.Table 2. has the summary of device performance of the compound 1～10 of device configuration B
Compound Trigger voltage (V) At 100cd/m 2Voltage (V) Maximum current efficiency (cd/A) Maximum external quantum efficiency (%) λ max EL(nm) CIE (x，y)
1 3.0 5.6 1.2 2.3 423 0.155，0.070
2 3.3 4.9 1.9 1.8 446 0.152，0.137
3 2.8 4.8 1.7 2.4 434 0.147，0.085
4 2.7 3.9 2.9 2.4 450/477 0.143，0.174
5 2.8 5.4 1.3 2.0 432 0.150，0.084
6 3.5 6.5 1.3 2.0 433 0.151，0.097
7 2.9 4.2 2.1 1.4 483 0.144，0.215
8 3.4 5.5 0.9 1.2 436 0.162，0.102
9 3.1 4.6 5.8 2.6 493 0.176，0.397
10 3.0 5.1 9.1 5.1 492 0.144，0.279
Table 3 has been described the energy level of compound 1～10.The energy level of table 3. illuminant compound 1～10
Compound 1 2 3 4 5 6 7 8 9 10
HOMO(eV) -5.11 -5.16 -5.10 -5.12 -5.14 -5.08 -5.14 -5.13 -5.17 -5.03
LUMO(eV) -2.15 -2.26 -2.20 -2.31 -2.14 -2.18 -2.28 -2.21 -2.39 -2.22
Band gap (eV) 2.96 2.90 2.90 2.81 3.00 2.90 2.86 2.92 2.78 2.81
Those of skill in the art are understandable that, many improvement that the exemplary of describing is in this article carried out are all possible.More properly, the invention is intended to all these improvement are encompassed in by in claims limited range.
All documents of quoting in this article all by reference integral body be incorporated herein.
Although disclose multiple embodiments of the present invention herein, according to those skilled in the art's common practise, can make many corrections and improvement within the scope of the invention.These improvement comprise in order in essentially identical mode, to reach identical result the replacement scheme for the known equivalence of either side of the present invention.Unless otherwise defined, all technology of using in this article and scientific terminology have the identical meanings of usually understanding with those of skill in the art of the present invention.

Claims (31)

1. the compound of a general formula (I):
Figure FDA00003228765400011
Wherein,
Ar 1For phenylene;
Ar 2And Ar 3Be 9,9-dialkyl group fluorenylidene, wherein said alkyl is side chain or the unbranched univalence hydrocarbyl with 1～18 carbon atom;
Ar 4And Ar 5Be phenylene and be connected to each other by singly-bound;
Ar 6And Ar 7Identical and be: phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9,9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl, 7-(4 '-cyano-phenyl)-9, in 9-dihexyl fluorenyl or following groups one:
Figure FDA00003228765400012
Figure FDA00003228765400021
Wherein, R, R ', R " and R " ' separately are independently halogen, cyano group, nitro, carbonyl, sulfinyl, alkylsulfonyl, alkyl, perfluoroalkyl or alkoxyl group, and q is 0～6 integer, and wherein said alkyl is side chain or the unbranched univalence hydrocarbyl with 1～18 carbon atom; With
M, n, p, r, s, x and y respectively do for oneself 1.
2. compound claimed in claim 1, wherein, Ar 6And Ar 7Identical and be: phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9,9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl, 7-(4 '-cyano-phenyl)-9, in 9-dihexyl fluorenyl or following groups one:
Figure FDA00003228765400031
3. compound claimed in claim 1, wherein, Ar 6And Ar 7Identical and be: phenyl, 4-trifluoromethyl, 2-naphthyl, 3-benzothienyl, phenanthryl, 9,9-dihexyl fluorenyl, pyrenyl, 9-phenyl carbazole base, 4-cyano-phenyl or 7-(4 '-cyano-phenyl)-9,9-dihexyl fluorenyl.
4. compound claimed in claim 1, wherein, Ar 6And Ar 7Identical and be in following groups:
Figure FDA00003228765400032
5. the described compound of any one in claim 1～4, wherein, described 9,9-dialkyl group fluorenylidene is 9,9-dihexyl fluorenylidene.
6. film, it comprises the described compound of any one according to claim 1～5.
7. film claimed in claim 6, wherein, the thickness of described film is about 0.1～about 1000nm.
8. claim 6 or film claimed in claim 7, wherein, described film further comprises material of main part.
9. film claimed in claim 8, wherein, described material of main part comprises: poly-(9-vinylcarbazole), 4, 4 '-N, N '-bis-carbazoles-biphenyl, 4, 4 ', 4 "-tri-(N-carbazole) triphenylamine, N, N '-phenylbenzene-N, N '-bis-(3-aminomethyl phenyl) (1, 1 '-phenylbenzene)-4, 4 '-diamines, N, N '-bis-(1-naphthyl)-N, N '-phenylbenzene-1, 1 "-phenylbenzene-4, 4 '-diamines, 4, 4 ', 4 " tri-(N, N-phenylbenzene-amino) triphenylamine, 1, 3, 5-tri-(diphenyl amino) benzene, 1, 3, 5-tri-(4-(two-2-pyridinylamino) phenyl) benzene, poly (p phenylene vinylene) derivatives, poly-fluorene derivatives, 3-phenyl-4 (1 ' naphthyl)-5-phenyl-1, 2, the 4-triazole, 2-(4-phenylbenzene)-5 (the 4-tertiary butyl-phenyl)-1, 3, the 4-oxadiazole, 2, 2 '-(1, the 3-phenylene) two [5-[4-(1, the 1-dimethyl ethyl) phenyl]]-1, 3, 4-oxadiazole or poly-[2-(6-cyano group-6-methyl) Oxy-1 in heptan, 4-phenylene].
10. claim 6 or film claimed in claim 7, wherein, described compound is as material of main part, and described film further includes organic dye or phosphorescent emitters.
11. film claimed in claim 10, wherein, described organic dye comprises: 10-(2-[4-morpholinodithio base)-1, 1, 7, 7-tetramethyl--2, 3, 6, 7-tetrahydrochysene-1H, 5H, 11H-[l] chromene also [6, 7, 8-ij] quinolizine-11-ketone, 3-(2-[4-morpholinodithio base)-7-(diethylin)-2H-1-chromen-2-one, 4-(the dicyano methylene)-2-tertiary butyl-6-(1, 1, 7, 7-tetramethyl-julolidine-9-thiazolinyl)-4H-pyrans, rubrene, 4-(the dicyano methylene)-2-tertiary butyl-6-(to the diphenyl amino styryl)-4H-pyrans, 3-(dicyano methylene)-5, 5-dimethyl-1-[(4-dimethylamino) styryl] tetrahydrobenzene, 6-methyl-3-[3-(1, 1, 6, 6-tetramethyl--10-oxo-2, 3, 5, 6-tetrahydrochysene-1H, 4H, 10H-11-oxa--3a-azepine benzo [de]-anthracene-9-yl) acryl] pyrans-2, the 4-diketone, 6, 13-phenylbenzene pentacene, (N-is to the amino) perylene or 1 of styryl phenyl-N-p-methylphenyl for 3-(N-phenyl-N-p-methylphenyl amino)-9-, the bisstyryl naphthalene derivatives that 1 '-dicyano replaces.
12. the described film of claim 6 or 7, it is standby with the solution coat legal system.
13. the described film of claim 12, wherein, described solution coat method comprises spin-coating method, teeming practice, intaglio plate coating method, excellent painting method, rolling method, coiling rod coating method, dip coating, spraying method, silk screen print method, flexographic printing method, offset printing method or ink jet printing method.
14. a device, it comprises anode, negative electrode and is arranged on the film that comprises the described compound of any one in claim 1～5 between this anode and negative electrode.
15. the described device of claim 14, wherein, described film is luminescent layer.
16. the described device of claim 15, it further comprises the hole transmission layer that is arranged between described luminescent layer and anode.
17. the described device of claim 16, wherein, described hole transmission layer comprises the mixture of polyaniline or poly-(3,4-Ethylenedioxy Thiophene) and poly-(styrene sulfonic acid).
18. the described device of any one in claim 16～17, it further comprises the hole injection layer that is arranged between described anode and hole transmission layer.
19. the described device of claim 18, wherein, described hole injection layer comprises 4,4 '-N, N '-bis-carbazoles-biphenyl, 4,4 '; 4 "-tri-(N-carbazole) triphenylamine, N, N '-phenylbenzene-N, N '-bis-(3-aminomethyl phenyl) (1,1 '-phenylbenzene)-4,4 '-diamines, N, N '-bis-(1-naphthyl)-N, N '-phenylbenzene-1; 1 "-phenylbenzene-4,4 '-diamines, p-phenylene vinylene or poly-fluorenes.
20. the described device of any one in claim 15～17, it further comprises the electron transfer layer that is arranged between described luminescent layer and negative electrode.
21. the described device of claim 20, wherein, described electron transfer layer comprises three (oxine) aluminium, 2-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole and 2,2 ', 2 "-(1; 3; 5-benzene three bases) three-[1-phenyl-1H-benzoglyoxaline], 3-phenyl-4 (1 ' naphthyl)-5-phenyl-1,2,4-triazole, 2; 2 '-(1; the 3-phenylene) two [5-[4-(1,1-dimethyl ethyl) phenyl]]-1,3; 4-oxadiazole or poly-[2-(6-cyano group-6-methyl) Oxy-1 in heptan, 4-phenylene].
22. the described device of any one in claim 15～17, it further comprises the hole blocking layer that is arranged between described luminescent layer and negative electrode.
23. the described device of claim 22, wherein, described hole blocking layer comprises 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline or 1,3,5-tri-(phenyl-2-benzimidazolyl-) benzene.
24. the described device of any one in claim 15～17, it further is included in the electron injecting layer that between described negative electrode and luminescent layer, next-door neighbour's negative electrode arranges.
25. the described device of claim 24, wherein, described electron injecting layer comprises lithium fluoride or lithium fluoride/aluminium.
26. the described device of claim 14, it further comprises the hole injection layer, the hole transmission layer that is close to this hole injection layer setting that are close to described anode setting, be arranged on luminescent layer between this hole transmission layer and described negative electrode, be arranged on electron transfer layer between this luminescent layer and negative electrode, be arranged on the hole blocking layer between this electron transfer layer and negative electrode and be arranged on the electron injecting layer between this hole blocking layer and negative electrode, and wherein the one deck at least in hole transmission layer, luminescent layer or electron transfer layer comprises described film.
27. a device, it comprises:
Anode;
Be arranged on the luminescent layer on this anode, this luminescent layer comprises the described compound of any one in claim 1～5; With
Be arranged on the negative electrode on this luminescent layer.
28. a device, it comprises:
Anode;
Be arranged on the hole transmission layer on this anode;
Be arranged on the luminescent layer on this hole transmission layer;
Be arranged on the electron transfer layer on this luminescent layer; With
Be arranged on the negative electrode on this electron transfer layer,
Wherein the one deck at least in hole transmission layer, luminescent layer and electron transfer layer comprises the described compound of any one in claim 1～5.
29. a device, it comprises:
Anode;
Be arranged on the hole injection layer on this anode;
Be arranged on the hole transmission layer on this hole injection layer;
Be arranged on the luminescent layer on this hole transmission layer;
Be arranged on the electron transfer layer on this luminescent layer; With
Be arranged on the hole blocking layer on this electron transfer layer;
Be arranged on the electron injecting layer on this hole blocking layer;
Be arranged on the negative electrode on this electron injecting layer,
Wherein the one deck at least in hole transmission layer, luminescent layer or electron transfer layer comprises the described compound of any one in claim 1～5.
30. the described device of any one in claim 14～17 and 26～29, wherein, described anode comprises gold and silver, tin indium oxide or conductive polymer coating.
31. the described device of any one in claim 14～17 and 26～29, wherein, described negative electrode comprises barium, calcium, magnesium, indium, aluminium, ytterbium, calcium silver alloys, Al-Li alloy or magnesium silver alloys.
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